{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/53935"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/53935","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Structure and microwave spectrum of the 2-cyano-2-propyl radical","abstract":"The rotational spectra of the 2-cyano-2-propyl and d⁶-2·cyano-2-propyl radicals were observed using a Stark modulated spectrometer. The radicals were generated in the gas phase by UV irradiation of sublimed azoisobisbutyronitrile. They were detectable in the cell for approximately one hour. Thirty-three transitions were assigned for (CH₃)₂CCN and twenty-one for (CD₃)₂CCN. The rigid rotor rotational constants determined by calculation of the hypothetical unsplit rotational transitions are A=8276.7, B=3919.7, C=2751.5Mhz for (CH₃)₂CCN and A=6241.3, B=3490.7, C=2372.6Mhz for (CD₃)₂CCN. A program to calculate the fine splittings and hyperfine splittings due to the ¹⁴N nucleus and six protons was written. The spin rotation constants determined for the two species were E<sub>aa</sub>=-69.9, E<sub>bb</sub>=-36.1, E<sub>cc</sub>=2.7Mhz and E<sub>aa</sub>=-55.4, E<sub>bb</sub>=-32.6 Mhz for (CH₃)₂CCN and (CD₃)₂CCN respectively. The hyperfine coupling constants for ¹⁴N are identical for both isotopic species and were found to be T<sub>aa</sub>=-17.2, T<sub>bb</sub>=-17.1 and T<sub>cc</sub>=34.4 Mhz. The proton and deuteron hyperfine splittings were not resolved. The structural parameters determined from an <r₀> fit of the moments are r<sub>CN</sub>=1.18A, r<sub>CC</sub>=1.42A, r<sub>CMe</sub>=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar.","abstract_html":"The rotational spectra of the 2-cyano-2-propyl and d⁶-2·cyano-2-propyl radicals were observed using a Stark modulated spectrometer. The radicals were generated in the gas phase by UV irradiation of sublimed azoisobisbutyronitrile. They were detectable in the cell for approximately one hour. Thirty-three transitions were assigned for (CH₃)₂CCN and twenty-one for (CD₃)₂CCN. The rigid rotor rotational constants determined by calculation of the hypothetical unsplit rotational transitions are A=8276.7, B=3919.7, C=2751.5Mhz for (CH₃)₂CCN and A=6241.3, B=3490.7, C=2372.6Mhz for (CD₃)₂CCN. A program to calculate the fine splittings and hyperfine splittings due to the ¹⁴N nucleus and six protons was written. The spin rotation constants determined for the two species were E&lt;sub&gt;aa&lt;/sub&gt;=-69.9, E&lt;sub&gt;bb&lt;/sub&gt;=-36.1, E&lt;sub&gt;cc&lt;/sub&gt;=2.7Mhz and E&lt;sub&gt;aa&lt;/sub&gt;=-55.4, E&lt;sub&gt;bb&lt;/sub&gt;=-32.6 Mhz for (CH₃)₂CCN and (CD₃)₂CCN respectively. The hyperfine coupling constants for ¹⁴N are identical for both isotopic species and were found to be T&lt;sub&gt;aa&lt;/sub&gt;=-17.2, T&lt;sub&gt;bb&lt;/sub&gt;=-17.1 and T&lt;sub&gt;cc&lt;/sub&gt;=34.4 Mhz. The proton and deuteron hyperfine splittings were not resolved. The structural parameters determined from an &lt;r₀&gt; fit of the moments are r&lt;sub&gt;CN&lt;/sub&gt;=1.18A, r&lt;sub&gt;CC&lt;/sub&gt;=1.42A, r&lt;sub&gt;CMe&lt;/sub&gt;=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar.","abstract_has_math":false,"creators":["Claytor, Robinson C. P."],"institution":"Virginia Polytechnic Institute and State University","degree_name":"Ph. D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Graybeal, Jack D."],"committee_members":["Field, Paul E.","Schug, John C.","Tanko, James M.","Viers, Jimmy W."],"year":1988,"date_issued":"1988","date_published":"1988","updated_at":"2026-07-22T22:19:45Z","subjects":[],"languages":["en_US"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/53935","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Graybeal, Jack D."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Field, Paul E.","Schug, John C.","Tanko, James M.","Viers, Jimmy W."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Claytor, Robinson C. P."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2015-06-29T22:07:12Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2015-06-29T22:07:12Z"]},{"key":"dc:date.issued","label":"Date","values":["1988"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute and State University"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/53935"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The rotational spectra of the 2-cyano-2-propyl and d⁶-2·cyano-2-propyl radicals were observed using a Stark modulated spectrometer. The radicals were generated in the gas phase by UV irradiation of sublimed azoisobisbutyronitrile. They were detectable in the cell for approximately one hour. Thirty-three transitions were assigned for (CH₃)₂CCN and twenty-one for (CD₃)₂CCN. The rigid rotor rotational constants determined by calculation of the hypothetical unsplit rotational transitions are A=8276.7, B=3919.7, C=2751.5Mhz for (CH₃)₂CCN and A=6241.3, B=3490.7, C=2372.6Mhz for (CD₃)₂CCN. A program to calculate the fine splittings and hyperfine splittings due to the ¹⁴N nucleus and six protons was written. The spin rotation constants determined for the two species were E<sub>aa</sub>=-69.9, E<sub>bb</sub>=-36.1, E<sub>cc</sub>=2.7Mhz and E<sub>aa</sub>=-55.4, E<sub>bb</sub>=-32.6 Mhz for (CH₃)₂CCN and (CD₃)₂CCN respectively. The hyperfine coupling constants for ¹⁴N are identical for both isotopic species and were found to be T<sub>aa</sub>=-17.2, T<sub>bb</sub>=-17.1 and T<sub>cc</sub>=34.4 Mhz. The proton and deuteron hyperfine splittings were not resolved. The structural parameters determined from an <r₀> fit of the moments are r<sub>CN</sub>=1.18A, r<sub>CC</sub>=1.42A, r<sub>CMe</sub>=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Structure and microwave spectrum of the 2-cyano-2-propyl radical"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Graybeal, Jack D."],"dc:contributor.committeemember":["Field, Paul E.","Schug, John C.","Tanko, James M.","Viers, Jimmy W."],"dc:contributor.department":["Chemistry"],"dc:creator":["Claytor, Robinson C. P."],"dc:date.accessioned":["2015-06-29T22:07:12Z"],"dc:date.available":["2015-06-29T22:07:12Z"],"dc:date.issued":["1988"],"dc:description.abstract":["The rotational spectra of the 2-cyano-2-propyl and d⁶-2·cyano-2-propyl radicals were observed using a Stark modulated spectrometer. The radicals were generated in the gas phase by UV irradiation of sublimed azoisobisbutyronitrile. They were detectable in the cell for approximately one hour. Thirty-three transitions were assigned for (CH₃)₂CCN and twenty-one for (CD₃)₂CCN. The rigid rotor rotational constants determined by calculation of the hypothetical unsplit rotational transitions are A=8276.7, B=3919.7, C=2751.5Mhz for (CH₃)₂CCN and A=6241.3, B=3490.7, C=2372.6Mhz for (CD₃)₂CCN. A program to calculate the fine splittings and hyperfine splittings due to the ¹⁴N nucleus and six protons was written. The spin rotation constants determined for the two species were E<sub>aa</sub>=-69.9, E<sub>bb</sub>=-36.1, E<sub>cc</sub>=2.7Mhz and E<sub>aa</sub>=-55.4, E<sub>bb</sub>=-32.6 Mhz for (CH₃)₂CCN and (CD₃)₂CCN respectively. The hyperfine coupling constants for ¹⁴N are identical for both isotopic species and were found to be T<sub>aa</sub>=-17.2, T<sub>bb</sub>=-17.1 and T<sub>cc</sub>=34.4 Mhz. The proton and deuteron hyperfine splittings were not resolved. The structural parameters determined from an <r₀> fit of the moments are r<sub>CN</sub>=1.18A, r<sub>CC</sub>=1.42A, r<sub>CMe</sub>=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar."],"dc:description.degree":["Ph. D."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/53935"],"dc:language.iso":["en_US"],"dc:publisher":["Virginia Polytechnic Institute and State University"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["Structure and microwave spectrum of the 2-cyano-2-propyl radical"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:45Z"}